Preparation of fluorocarbons



.ficult to synthesize.

United States Patent-- 2,980,739 PREPARATION or FLUOROCARBONS Mark Wendell Farlow, Wilmington, 'Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, 'DeL, a corporation of Delaware No Drawing. Filed Oct. 6, 195 8, Ser. No. 765,331 20 Claims. cum-653.3

fluoroethylene and cyanogen fluoride. s The technical importance of fluorocarbons is constantly increasing. Tetrafluoroethylene in particular is 2,980,739 Patented Apr. 18, 1961 v r 2 thus is not ableto create the most favorable conditions for the form ti not the desired products.

"There therefore a need for an improvement in the high.temperatu're synthesis of fluorocarbons, especially tetrafluoroethylene, and other fluorine-containing carbon carbon and fluorides, whereby the necessary earbaiw ma s me present in elemental form, but would be supplied instead-by an added volatile reactant capable ofmalcing intimatecontact with the gaseous fluoride in'any desired relative proportions.

'nyention is a process of preparing fluorine-contairiing carbon compounds which comprises heating to a ticular, it relates to a new process ofsynthesizing tetraof such high industrial interest that new and improved methods of synthesizing it are actively being sought. As

to cyanogen fluoride, FCN, it is a little known, virtually unstudied compound which has heretofore been very dif- It is a'gas (B.P. 44 C.) which can be used as a fumigant and disinfectant on account of its toxicity. Its trimer, cyanuric fluoride (FCN) is more reactive than the well-known cyanuric chloride and is therefore highly suitable for the preparation of valuable cyanuric esters. i I v A recent technical advance'in the field of carbonfluorine temperature ofat least 1500 C. a mixture of (a) a fluoride of a non-metallic element of groups IV, V, VI and'VII of the'periodic table having an atomic number from 6 to 53, inclusive, and (b) a compound of the class cohsisting of carbon-nitrogen compounds and carbonnitrogen-hydrogen compounds, said compound boiling below 300 Cpa t atmospheric pressure and coolingv the gaseous reaction product within not more than one second to a temr'aera'turebelow 500 C.

This reaction yields a mixture of carbon-fluorine compounds, thefrnajor components of which are fluorocarports, especially tetrafluoroethylene and carbon tetrafluoride, withlesser amounts of hexafluoroethane and sun lesser','amounts of" other saturated or unsaturated fluorocarbons'. Carbon fluorine nitrogen compounds,

compounds is the discovery that fluorocarbons eah he I with elemental carbon at high temperature, "ei.g., ina

carbon arc, and that tetrafluoroethylene is present in very substantial amounts in the fluorocarbon product' when I s I s I that r'nay be presentin" the system is converted to hydrolowing contact with the hot carbon. These developments 7 have been published in a series of United States patents,

principally 2,709,182, issued to M. W. Farlow on May '24, 1955; 2,709,186 to 2,709,191 inclusive, issuedio M. W. Farlow et al. on May 24, 1955; 2,709,192, issued to M. W. Farlow on May 24, 1955 2,725,410, issued to .M. W. Farlow et al. on November 29, 19 55, and 2,732,;

410-11, issuedto M. W.'Farlow et al, on January 2 1,

These high temperature processes. constitute alrilajor improvement in the field of fluorocarbon synthesis; However, they are not free'of technical difficulties, e' spes ,7

" pets is "not'objectionable, the'hydroge'n fluoride can be cially with respect to continuous operation. When elemental carbon is [consumed in-a continuous process,- it

, must be replaced continuously; This requirement "difficult to meet, particularly when the" source of heatis a carbon arc, a preferred embodiment of these processes because of the very high temperatures which are readily attainable by means of an arc.. With a carbon arc, some or all of the necessary carbon is supplied by the electrodes themselves, and consumption of carbon fr'om'the I electrodes presents diflicult engineering'problems which interfere with continuous operation on a large scale.-

Even when the operation is carried out in an externally heated reactor; such as a tube ofrefractory material heated in a suitable furnace the use of elemental carbon and the solid carboninay not be adequate, and the open. ator has little or no control over the proportionof carprincipally cyanogen fluoride and cyanuric'fluoride, are generally present in minor amounts, although under certainlconditions, for example, when the carbon-nitrogen reactant is used i n high ratios relative to the fluoride ant, cyanogen fluoride can form a substantial pro,- p 1011 of the reaction product. The crude reaction prodiietrnay also contain some unreacted fluoride, which can e"recycled, and the free element whose fluoride was employed, or compounds thereof. i

In thisreaction, most or all of the combined hydrogen gfen fluoride, thus consuming part of the available fluo- NY This side reaction is unavoidable when the carhon-supplying compound contains hydrogen, butit should minimized to the extent possible. For this reason, asvvell as .for reasonsfof better operability, the fluoride employed should contain no hydrogen. For the same reason, the carbon-supplying reactant should contain a minimum amount of'hydrogen and the reactants should 7 recovered assodium fluoride by scrubbing the gaseous re-.

action product witl'i'aqueous sodium-hydroxide or sodium carbonate. treatment does not" affect the fluorocarpens, which "are resistant to hydrolysis. The sodium fluoride so obtained can be converted to carbon tetrafluoride in excellent yields by reacting it with carbon and chlorine at a temperature in the range ofl200-l700 C., and the carbontet'rafluoride can'be recycled to give tetraiiuoroethyleneby the process of this invention, orfbyreaction with'hot elemental carbon .as disclosedin the aforementioned ULSQPatent 2,709,192. fiflAnother rneth of recovering the hydrogen fluoride, whichdoes"notinvolve hydrolysis of the water-sensitive reaction'products, consists in bring the gaseous products 2 contact with an alkali metal fluoride, particularly hon relative to thefluoride at any given moment, and

sodiuni'fluoride, which absorbs the hydrogen fluoride throughtormation ot a non-volatile alkali metal bi The fluorides'suitable for, use in this process are the it? J; g ,4

hydrogen-free fluorides of those non-metallic elements in groups IV to VII of the periodic table which have atomic numbers from 6 to 3, inclusive. These non-metallic elements are found in subgroup A of groups 'IVto VII of the periodic table. Reference is made here to Demings periodic table, as given in Demings General Chemistry (John Wiley & Sons, Inc., 5th ed, pp. 11-4 3,), and in many other reference books such-as the Handbook of Chemistry and Physics, published by the Chemical Rubber Publishing Co. This table'shows that the non-metallic elements are, besides the rare gases, the elements of group VII-A (i.e., the halogens); those in group Vl Ahaving atomic numbers 8 to 52; those in group V-Ahaving atomic numbers 7 to 33; those in group'IV-A having atomic numbers 6 to 14; and boron in group III-A. Of these non-metallic elements, those in groups IV to VII which have atomic numbers 6 to' 53 (i.e., carbon, silicon, nitrogen, phosphorus, arsenic, oxygen, sulfur, selenium, tellurium, fluorine, chlorine, bromine and iodine) are the elements whose fluorides are operable in this'process. Thus, for example, the suitable fluorides including the carbon fluorides (fluorocarbons) free fromaliphatic unsaturation, particularly CE, and C 'F the silicon fluorides, particularly SiFgnitrogen trifluon'de, phosphorus pentafluoride, arsenic trifluoride, and sulfur fluorides (SP and SP fluorine itself, chlorine triflu olride, iodine pentafluoride, etc. Fluorides in which more than one of the above-listed elements are combined with the fluorine; such as carbonyl fluorine, sulfuryl fluoride and'thionyl fluoride, are also suitable. J; j

For reasons of accessibility, ease of handling-and good results, the preferred starting materialsa're' elemental fluorine and the binary fluorides of the nonmetallic elements in groups IV-A, V-A and VI-Aof the periodic table. The most useful and' preferred fluorides are the aliphatic, saturated fluorocarbons of one to two carbon atoms (carbon tetrafluoride and hexafluoroethane),silifluoride and carbon-supplying reactant are chosen so that the ratio of total combined carbon to total fluorine in the reacting system is at least 0.1:1, preferably at least 0.25:1. At the same time, in order to minimize the con tetrafluoride, phosphorus pentafluoridqarsenic trlfluoride, sulfur tetrafluoride and'sulfurhexafluoride.

The carbon-supplying reactant, can be"'any volatile (boiling below about 300 Ci at atmospheric pressure, i.e., 760 mm. of mercury) compound ofcarbon and nitrogen, orof carbon, nitrogen and'hydrogen. It is desirable that' the atomic ratios of carbon to hydrogen and nitrogen to hydrogen in the hydrogen-containing carbon supplying reactants be as high as possible, both in order tofavor a higher rate of formation of carbon-fluorine and carbon-fiuorine-nitrogen compounds per unit volume, and to minimize the formation of hydrogen fluoride. Thus, while reactants in which the C/H ratio is as low as 0.166(1 (e.g., methylhydrazine) and the N/H ratio is as low as 0503751 (e .g.,' tributylamine) are operable,' it is preferred to .use reactants in which the C/H ratio is at least 0.25:1 and the N/H ratio at least'0. 1:1. j

Among the suitable volatile carbon-supplying reactants formation of hydrogen fluoride, it is desirable that the ratio of the total fluorine to the total combined hydrogen in the reacting system to be at least 1.5:1, preferably at least 3:1. r

' The reaction conditions are essentially those described in the patents already referred to for the synthesis of tetrafluoroethylene. Thus the reaction temperature should be at least 1500 C., and it can be as high as can be obtained by practical means, for example in the temperature range of the electric arc, which is estimated to be 2500-4000 C. or even higher.

The absolute pressure of the reactant gases during the pyrolysis is not critical. In general, however, it is much preferred to operate at reduced pressures,which can be as "low as 1 mm. of mercury, butare desirably in the range of 10-300 mm. of mercury. This is especially desirable when an electric arc is used as the source of heat, since the operation of'the ar'c becomes much more diflicult with increase in pressure. With other types of reactors, e.g., with externally heated tubular reactors, the absolute pressure is also much preferably subatmospheric ('e.g., in therange of. 10-300 mm.), but it can be atmospheric or even superatmospheric; I

Practical conversions to the chiefly desired products,

i.e., tetrafluoroethylene and cyanogen fluoride, can be perature not exceeding 500 0, preferably of the order of 400 C. or lower. The time required tocoolthe gaseous reaction product, that is, the time of transition from the reaction temperature to a temperature of j about 400- 500 Q, should not exceed one second. Preferably, it is in the range of 0.001 to 0.1 second. The optimum rate of flow'through the hot reaction zone of the gaseous reactants depends in large part on this quenching requirement, that is, on the efliciency of the quenching system. Reduced pressures facilitate rapid quenching in any given form of apparatus.

The necessary quenching can be achieved in various ways. For example,.the off-gas upon leaving the hot reaction zone can be made to pass over the outside wall of a metal vessel containing a coolant material such as water, solid carbon dioxide or liquid nitrogen and located a short distance from. the reaction zone, or the oif-gas can be passed through a double-walled hollow cylinder wither-without radial fins, cooled with circulating water. In another modification, the off-gas is carried immediately fromthe hot zone into a suitably designed quench reactor where it' comes in intimate contact with a finely may be mentioned cyanogen, hydrogen'cy'anide, 'diazo methane, methylhydrazine, phenylhydrazinerarnines such as methylamine, ethylamine, n-propylamine', isobutylamine, n-hexylamine, n-octylamine,dimethylamine, diethyl amine, trimethylamine, triethylarnine, tri-n-butylamine, ethylenediamine, tetramethylenediamine, aniline, N-methylaniline, benzylarnine,.etc'.; nitriles such as acetonitrile, propionitrile, butyronitrile, malononitrile, acrylonitrile, fumaronitrile, ben zonitrile, benz yl cyanide, etc., heterocyclic compounds such as ethylenamine, N-methyl ethylenimine pyrrol, pyridine, ethylpyridine, piperidine, piperazine, pyrimidine, etc.;' and the like. Both because they have lower boiling points and because they have higher C/H ratios, the preferred carbon -supplying'reactants are those having from 1 to 4 carbon atoms.

The relative proportions of fluoride and carbon-supplying reactant are not critical. They are important only to the extent that maximum utilization of the fluorideand at the same time minimum formation of hydrog en fl uo ride are desired. In practice, the relative amounts of divided"(fluidized) solid, which is advantageously carbon. "Apparatus of any 'suitable design can be used to carry out thep'rocess of this invention. n For example, the r actorcan be a tube of refractory material, if desired packdlwithparticles of an appropriate infusible 'substance to improve contact between the reactants, through whichis passed a mixture inv the desired proportions of the; gaseous or-vaporized fluoride and carbon-supplying reactant, .The tube is heated toat least 1500 C. ina resistance-furnaceor induction furnace, and appropriate means are provided to quench the otf-gas and collect the reaction products. .Inlthis type .of equipment, however, in' view of the corrosive nature of manyfluorides and reaction by-products at the high temperatures involved,

it is often desirable'tousecarbon or graphite as the ma teri-al' of construction for the hot parts of the reactor and as the contact masses. 'S omeiof this carbon participates in the reaction, in spite of the fact that most ofjthe carbon will'be furnished-flay 'theadded volatile carbon compound; Thus, .while' the use of a carbon snpplying reactant isadvantageous even in an apparatus made of, or containing rier gas such as nitrogen or .5 carbon, the full advantages of the process are not realized in suchacase. f

A preferred device for carrying out the process is the electric arc, which produces extremely high temperatures. In this type of apparatus, the electrodes can be made of a heatand corrosion-resistant metal, suchas copper or tungsten, thereby contributing no carbon to the reaction. In addition, metal electrodes can be kept relatively cool through internal circulation of a cooling liquid, and under such conditions they remain substantially unattached for considerable periods of time. Carbon electrodes are also entirely'suitable, and a carbon arc can be used even withbut special provisions for preventing or decreasing electrode consumption, since even in such a case a very substantial amount of the necessary carbon is supplied by the added volatile carbon compound rather than by the electrodes. However, here again the full advantages of the process are realized only when essentially non-consumable carbon electrodes are used. A carbon anode can be made essentially non-consumable by maintaining it at a relatively low temperature, in practice below about 1500 C. This can be accomplished by using a relatively thin anode supported by, and in intimate contact with, a watercooled metallic holder, this device providing very efiicient external cooling of the carbon anode. In a low tension arc the cathode cannot be similarly cooled since its temperature must be high enough to sustain thermal emission of electrodes, but the cathode norm'allyfurnishes little or no carbon. With a cool anode, a carbon electrode system loses substantially no carbon, as can be demon: strated by weighing the electrodes before and after'operating the arc. a

Improved forms of carbon'arc for the synthesis of fluorocarbons. are described in' the aforementioned US.

Patent 2,709,192 and in other patents. These are suitable I for use in the present process,'with such appropriate modifications as may be required for. the cooling of the electrodes, if this is desired, and for the introduction of the carbon-supplying reactant. 'The latter is preferably introduced in the gaseous or vaporized form, if desired premixed with the gaseous or vaporized fluoride in the desired proportions, but it can also be delivered as a'liquid or even as a solid into the. reaction, where it'vaporizes before entering the arc zone. A substantially inert carheh'um can be used-if :de-

sired. 5 a

An especially suitable type of electric 'arc,'for use in this process is a magneticallyrotated electric are] In .comparison with static arcs of conventionaldesign or even with the improved arcs of the kind mennmiefaabove, a rotating arc is far more efiicient by virtue of its much greater stability and of the fa'r better contact between arc and reactants that it permits. The-examples which follow were carried out using an arc of this type.

A particularly eflicienttype of rotating carbonlar c operates as follows: the reactants (fluorine and carbon- I supplying compound) pass through asymmetrical annular gap formed by a substantially cylindrical solid graphite cathode and a substantially cylindricalhollow graphite anode, wherein a continuous electrical discharge The electrical characteristics of the rotating are are essentially similar to those of the static arc. Thus, operating conditions of thearcmay be varied over a wide range from the minimum voltage required to maintain the arc to very high voltages,- e.g.,'in the range of- 10-75 volts. in general, for :a given current the required voltage of the arc is determined by the pressure in the system,

the width of the arc gap and the nature of the gases present in the arc chamber. The power requirements'will, of course, dependonthe quantity of reactants passed through the rotating arcand the temperature to which they are to be heated. v

The arc may be operated with a direct current or with an alternating current if the alternating; current. is of high frequency and is employed in combination with an alternating magnetic field which is in phase with the-arc current. A direct current is greatly preferred, since only .With a direct current is it possible to obtain a truly continuous rotating arc. resulting in uniform'heating-and high stability. Currentintensities in the range of-500 amperes are generally used;v

formed when the carbon-supplying reactant contains hy-' .drogen. The crude reaction product can be given .-a preliminary'treatment to. remove the hydrogen fluoridejfor example by bringingv itincontact with sodium fluoride. With or without prior removal of the hydrogen fluoride, the various ingredients (:tetrafluoroethylene, otherfiuorocarbons, cyanogen fluoride, cyanuric.:fluoride, etc.) can be isolated'by passing the gaseousreaction'product through cold condensersandfractionating the condensate through etficient distilling columns i The following examples illustrate the greater detail. 1 Y

. Example?" A" gaseous mixtureiof carbon tetrafluorideahd-cyanov gen in the molar ratio CF :(CN) of -2:1 was passed through a magnetically rotated carbon arc'at' an absocury. The cathode was a graphite rod, in diamete r,-: and the anodewas a hollow graphite cylinder-hay,- j

inganinternal diameter of 0.5; mounted on a water? cooled ring-shaped copper holder which served to keep 49:. amPereS-r T a t. as s e er. Pa si through the arc flame in the annular space between the Q Q cooled t rnally. b mea .e l id n t e An O the u by m ss ct gscc y nd cated 1 is rotated by magnetic lines of flux essentially parallel to'the axis of rotation of the annular are. This causes the arc to move at right angle tothe nagnetic fieldlglines. The magnetic field is created by ,surrounding the arc chamber with acoil through which a current (preferably g. the; ppar us jr o edu e .q Exam e a a direct current) passes. A fieId strength suitable to cause rotation is 100-2 0O gausses. "Ihe arcrotatesextremely rapidly in the annular gap between the electrodes, its speed being estimated at 1'0QO -l ),0QQi;revolu tions per second, and it heats the reactants m uniformly to extremely high temperatures as theyapass thr'oughthe gap. The gaseous reaction product leaves the arc chamber through the .hollow anode and isirnmediately cooled by contact with cold portions" o'f-the a aratus or with a specially designedgquenching l theanodecool. The arc was operated at '30 -volts'and electrodes, left the hot-reactiongone through the hollow anode and encountered a water-cooled copper surface about one inch downstream from thearc-gone, Where the gaseous reaction pr'oduct'was' quenched to below 590 within a few microseconds following contact with the arc flame. a

' The c n le r t; o me at the rat afabpui g. per hour, was collected in a copper trap' which that itconsisted chiefly of 'fluor ocarbons inthe' following molar proportions'i tetrafluoroethylene, 64%; carbon tetrafiuoride, 22%; higher fluoroca'rbons, 6%, Inaddition,

.the product contained cyanogen fluoride,z'cyanuric 'fluoride, trifluoroacetonitrile and cyanogen, with some (11ncondensed) nitrogen. I

a e 1 X mixture pf carbon tetrafluoride and hydrogen, cyanide in the molar ratioCFgHCN of 1.8:l was passed through 'the arc and .the' product was collected attherate of about 32 g. per hour.z,The reaction"'product containedsrnall -.am un f. hy e u r e i b m and-in tme t c p s, b t m i r'n d ts w re fluqrqcar ns the ll w n m la prd q cns t usresthy ene 5 carbon tet fli s hi h riflu g axbqn invention in the phosphorus pentafluoride.

Example 111 "The apparatus used was essentially that of Example I, except that the quenching surface was cooled with liquid nitrogen, the pressure within the arc chamber was 88 mm. of mercury and the arc was operated at 54 volts and 40 amperes. The reactants were'carbon tetrafluoride. and cyanogen but the latter was used in higher proportions than inExample I, the molar ratio CF :(CN) being 1:1.25; Nitrogen was used as a carrier gas, the rate of flow per minute being 575 ml. of nitrogen, 100 ml. of carbon tetrafluoride and 125 ml. of cyanogen, all at standard temperature and pressure.

Under-these conditions, carbon-fluorine-nitrogen prod ucts were formed in substantial amounts. The product, exclusive of nitrogen, contained, on a molar basis, 49% of tetrafluoroethylene, 23% of cyanogen fluoride, 5% of hexafluoroethane, 6% of carbon tetrafiuoride, 8% of cyanogen and 5% of trifiuoroacetonitrile. The electrodes were found to have lost no weight, indicating that all of the necessary carbon was derived from the cyanogen.

Example IV The apparatus was essentially similar to that of Example HI. The are was operated at 34 volts and 35 amperes, and the pressure within the arc chamber was 80-84 mm. of mercury. The reactants were phosphorus pentafluoride and cyanogen in 1:1 molar ratio, and nitrogen was used as a carrier gas, these ingredients being passed through the are at a fl'owrate per minute of 120 ml. of nitrogen, 100-ml. of PF;, and 100 ml. of (CN); 7

at standard temperatureand pressure.

In'this reaction, phosphorus trifiuoride is a major product since two of the fluorine atoms in phosphorus pentafluoride are much more. reactive than the other three.

The reaction product, exclusive of nitrogen, was found to contain, on a molar basis, of phosphorus trifiuoride,z6.4% of cyanogen, 1.6% of carbon tetrafluoride, 4.7% of tetrafluoroethylene, 0.7% of other fluorocarbons and 0.2% of cyanogen fluoride. There were also present some silicon tetrafluoride and some-chlorofluorocarbons, derived-fromhydrogen chloride impurities. in The graphite electrodes showed no loss in weight.

'Similar results were obtained when the graphite electrodes were-replaced by a copper anode and a tungsten cathode.

Example V The apparatus used was essentially that of Example 1H except that provision wasincluded to injectcyanogen directlyinto the arc flame from water-cooled orifices to minimize p'r'edecomposition'j The are was operated at 44 volts and 41 amperes, and the pressure within the arc chamber was 62-70 mm. of mercury. The reactants were sulfur, tetrafluoride and cyanogen in'approxirnately- 1:1.6 molar ratio with excess nitrogen used as a carrier gas and toreduce'contac't time with. the. arc. The reactants were passed through the arc at a flow rate, per minute, of 75 ml. ofsulfur tetrafluoride, ml. of cyanogen, and 425 ml. of nitrogen at standard temperature and pressure. Y

The product, exclusive of nitrogen, 'contained. on a molar basis, 19% of tetrafluoroethylene and 20 %,of cyanogen fluoride, alongwith 16% of carbon disulfide,

6% of carbon tetrafluoride, 25%, ofv cyanogen, 6% of trifluoroacetonitrilaaand other products inminor amounts.

foregoing examples are 1 action products, there may be -used hex'afluoroethane,

silicon tetrafluoride, arsenic trifiuoride, sulfur hexafluoride, fluorine, chlorine trifiuoride, or nitrogen trifiuoride as thefluoride component and,. diazomethane, methylhydrazine, n-propylamine, aniline, acrylonitrile, propionitrile orbenzonitrile as the. carbon-supplyingcomponent of the reaction mixture.

I claim: Y 1. A process for the preparation of fluorine-containingcarbon compounds which comprises heating .to a temperature of at least 1500 C. a mixture of (a) a fluoride of a non-metallic element of groups IV to VII of the periodic table, having an atomic number from 6,.to 53inclusive, and (Ma compound of the class cou sisting ofcarbon-nitrogen Compounds and carbon-nitrogen-hydrogen compounds, said compound boiling below 300 C. at atmospheric pressure, said carbon and nitrogen, or carbon, nitrogen and hydrogen, being the only elements in said compounds, and cooling .the gaseous reaction product to a temperature below 500 C. in less than one second.

2. A process for the preparation of fluorine-containing carbon compounds which comprises heating to a temperature of at least 1500 C. a mixture of (a) a fluoride of a non-metallic element of group IV of the periodic table having an atomic number of 6 to 14 inclusive, and (b) a compound of the class consisting of carbon-nitrogen compounds and carbon-nitrogen-hydrogen compounds boiling below 300 C.'at atmospheric pressure, said carbon and nitrogen, or carbon, nitrogen and hydrogen, being the only. elements in said compounds, and cooling the gaseous reaction product to a temperature below 500 C. in less than one second.

3. The process, as setforth in claim 2 wherein the non-metallic element is carbon. f

'4. The process as set forth in claim 3 wherein the fluoride of carbon is carbon tetrafluoride.

5.'The process as setforth in'claim 3 wherein the fluoride of carbon is hexafluoroethane. 6. The process as set forth in claim 2 wherein the non-metallic element 'is silicon.

7. A process for the preparation of fluorine-containing. carbon compounds which comprises heating to a temperature of at least 1500 C. a mixture of (a) a fluoride of a non-metallic element of group V of the periodic table having an atomic number .of 7- to 33 inclusive and (b) a compound of the class consisting of carbon-nitrogen compounds and carbon-nitrogenhydrogen compounds, boiling below 300 C at atmospheric pressure, said carbon and nitrogen, or carbon, ni-

trogen and hydrogen, being theonly elements in said compounds, and cooling'the gaseous reaction products toa'temperature below 500 C. in less than one second.

8. The'process as set forth in claim 7 wherein'the non-metallic element in nitrogen. I

9. The process as set forth in claim 7, wherein the non-metallic-element is arsenic.

10. The process as set forth in claim 7 wherein the non-metallic element is phosphorus.

'11. The process as set forth in claim 10 wherein the fluoride of phosphorus is phosphorus pentafluoride.

12; A [process for the preparation of fluorine-containing carbon compounds which comprises heating to a temperature of at least 1500 C. a mixture of-(a) a fluoride of a non-metallic element of group VI of the periodic table having an atomic number of 8 to 52 in,- clusive, and (b) a compound of the class consisting of carbon-nitrogen compounds and carbon-nitrogen-hydrogen compounds boiling below 300 C. at atmospheric pressure, saidcarbon and nitrogen, or carbon, nitrogen and hydrogen, being the only elements in said compounds, and cooling the gaseous reaction products to a temperature below 500 C. in less than one second.

13.1 The process as set forth in claim 12 wherein the non-metallic element is sulfur. f

1 14. The process as set forth in claim 13' wherein the fluoride of 'sulfu'r'is sulfur tetrafluoride.

15. The process for the preparation of fluorine-containing carbon compounds which comprises heating to a temperature of at least 1500 C. a mixture of (a) a fluoride of a non-metallic element of group VII of the periodic table having an atomic number of 9 to 53 inclusive, and (b) a compound of the class consisting of carbon-nitrogen compounds and carbon-nitrogen-hydrogen compounds boiling below 300 C. at atmospheric pressure, said carbon and nitrogen, or carbon, nitrogen and hydrogen, being the only elements in said compounds, and cooling the gaseous reaction product to a temperature below 500 C. in less than one second.

16. The process as set forth in claim 15 wherein the fluoride of the non-metallic element is fluorine.

17. A process for the preparation of tetrafluoroethylene which comprises passing through an electric carbon are a mixture of (a) a fluoride of a non-metallic element of group IV to .VII of the periodic table having an atomic number of 6 to 53 inclusive, and (b) a compound consisting of carbon and nitrogen and having from 1 to 4 carbon atoms and cooling the gaseous reaction products to below 500 C. in less than one second.

I0 18. The process as set forth in claim 17 wherein the carbon-nitrogen compound is cyanogen.

19. A process for the preparation of tetrafluoroethylene which comprises passing through an electric carbon are a mixture of (a) a fluoride of a non-metallic element of groups IV to VII of the periodic table having an atomic ntunber of 6' to 53 inclusive, and (b) a compound consisting of carbon nitrogen and hydrogen and having from 1 to 4 carbon atoms and'cooling the gaseous reaction products to below 500 C. in less than one second.

20. The process as set forth in claim 19 wherein the carbon-nitrogen-hydrogen compound is hydrogen cyanide.

References Cited in the file of this patent UNITED STATES PATENTS 2,709,186 Farlow et a1. May 24, 1955 2,732,410 Farlow et a1 Jan. 24, 1956 2,732,411 Farlow et al Jan. 24, 1956 2,773,089 Anderson Dec. 4, 1956 2,859,245 Smith Nov. 4, 1958 UNITED STATES-PATENT OFFICE CE-RTlFl'GA'llGN 0F CORREC'HQN Patent Not. 2 980 739 April 18 196.1

Mark Wendell Farlow It is hereby certified that error appears in the above numbered patent requiring correctionend. that the said Letters Patent should read as corrected below.

Column l line 67 after 'mnst insert also a column 2 line 6'7 for 'bring" read bringing eolumn 4 line 7 strike out "to"; column E5 line 28 for "'eleetrodesl read electrons line 41:3 for 'reaetion read reactor Signed and sealed this 5th day of September 139619 (SEAL) Attest:

ERNEST W. SWI'DER DAVID L. LADD Attesting Officer v Commissioner of Patents 

1. A PROCESS FOR THE PREPARATION OF FLUORINE-CONTAINING CARBON COMPOUNDS WHICH COMPRISES HEATING TO A TEMPERATURE OF AT LEAST 1500*C. A MIXTURE OF (A) A FLUORIDE OF A NON-METALLIC ELEMENT OF GROUPS IV TO VII OF THE PERIODIC TABLE, HAVING AN ATOMIC NUMBER FROM 6 TO 53 INCLUSIVE, AND (B) A COMPOUND OF THE CLASS CONSISTING OF CARBON-NITROGEN COMPOUNDS AND CARBON-NITROGEN-HYDROGEN COMPOUNDS, SAID COMPOUND BOILING BELOW 300*C. AT ATMOSPHERIC PRESSURE, SAID CARBON AND NITROGEN, OR CARBON, NITROGEN AND HYDROGEN, BEING THE ONLY ELEMENTS IN SAID COMPOUNDS, AND COOLING THE GASEOUS REACTION PRODUCT TO A TEMPERATURE BELOW 500*C. IN LESS THAN ONE SECOND. 